Self-assembled Nanoparticle Arrays Research Articles

High-Power Impulse Magnetron Sputter Deposition of Ag on Self-Assembled Au Nanoparticle Arrays at Low-Temperature Dewetting Conditions.

Plasmons have facilitated diverse analytical applications due to the boosting signal detectability by hot spots. In practical applications, it is crucial to fabricate straightforward, large-scale, and reproducible plasmonic substrates. Dewetting treatment, via applying direct thermal annealing of metal films, has been used as a straightforward method in the fabrication of such plasmonic nanostructures. However, tailoring the evolution of the dewetting process of metal films poses considerable experimental complexities, mainly due to nanoscale structure formation. Here, we use grazing-incidence small- and wide-angle X-ray scattering for the in situ investigation of the high-power impulse magnetron sputter deposition of Ag on self-assembled Au nanoparticle arrays at low-temperature dewetting conditions. This approach allows us to examine both the direct formation of binary Au/Ag nanostructure and the consequential impact of the dewetting process on the spatial arrangement of the bimetallic nanoparticles. It is observed that the dewetting at 100 °C is sufficient to favor the establishment of a homogenized structural configuration of bimetallic nanostructures, which is beneficial for localized surface plasmon resonances (LSPRs). The fabricated metal nanostructures show potential application for the surface-enhanced Raman scattering (SERS) detection of rhodamine 6G molecules. As SERS platform, bimetallic nanostructures formed with dewetting conditions turn out to be superior to those without dewetting conditions. The method in this work is envisioned as a facile strategy for the fabrication of plasmonic nanostructures.

Shrinking gap between nanoparticles in gold nanofilms to enhance Surface-Enhanced Raman Spectroscopy performance investigated by both experimental and theoretical methods

Sensitive and reliable interfacial self-assembled nanomembranes are widely used for the detection of chemical contaminants in food and environment. This study developed a high-performance Surface-Enhanced Raman Spectroscopy (SERS) analytical platform by self-assembling Au nanoparticles (AuNPs) at the three-phase liquid–liquid interface. The assembled nanoparticles arrays were immersed in halogen ions solution and the nanoparticle gaps were further shrunk through electrostatic interactions, resulting in a large-scale array of closely packed nanoparticles. The average gap between adjacent nanoparticles was less than 3 nm, where dense SERS ‘hot spots’ were generated and used for highly sensitive detection. The homogeneity of the self-assembled nanoparticle arrays under different conditions was still guaranteed despite the reduced integration time and the number of times in the mapping face sweep of the Au arrays. The improved high-throughput fabrication of self-assembled nanoparticle arrays in this way holds great promise for the development of a sensitive and reliable SERS platform for chemical contaminant monitoring.

Self-Assembling Systems for Optical Out-of-Plane Coupling Devices.

Micromirrors are used in integrated photonics to couple extraplanar light into the planar structure of a device by redirecting light via specular reflection. Compared with grating or prism-based couplers, micromirrors allow for coupling of light over a broader range of wavelengths, provided that the micromirror is fabricated with a specific 3D shape to ensure proper reflection angles. In principle, self-assembly methods could enable reliable, parallelizable fabrication of such devices with a high degree of precision by designing self-assembling components that produce the desired microscale geometry as their thermodynamic products. In this work, we use DNA-functionalized nanoparticles to assemble faceted crystallites with predetermined crystal shapes, and demonstrate with microscale retroreflectance measurements that these self-assembled nanoparticle arrays do indeed behave like optically flat mirrors. Furthermore, we show that the tilt angle of the micromirrors can be intentionally controlled by altering the crystallographic symmetry and preferred crystal orientations as a function of the self-assembly process, thereby altering the resulting specular angle in a programmable manner. Measurements of optical coupling from normal incidence into the substrate plane via an optical fiber confirm that the faceted structures can function as optical out-of-plane coupling devices, and coating these structures with reflective materials allows for high efficiency of light reflection in addition to the angular control. Together, these experiments demonstrate how self-assembled nanoparticle materials can be used to generate optically relevant architectures, enabling a significant step in the development of self-assembly as a materials fabrication tool for integrated optical devices.

Facile Detection and Quantification of Acetamiprid Using a Portable Raman Spectrometer Combined with Self-Assembled Gold Nanoparticle Array

Rapid and facile determination of pesticides is critically important in food and environmental monitoring. This study developed a self-assembled gold nanoparticle array based SERS method for highly specific and sensitive detection of acetamiprid, a neonicotinoid pesticide that used to be difficult in SERS analysis due to its low affinity with SERS substrates. SERS detection and quantification of acetamiprid was conducted with self-assembled gold nanoparticle arrays at the interface of chloroform and water as the enhancing substrate. Since targets dissolved in chloroform (organic phase) also have access to the hot-spots of Au NP array, the developed method exhibited good sensitivity and specificity for acetamiprid determination. Under the optimal conditions, SERS intensities at Raman shifts of 631 cm−1 and 1109 cm−1 displayed a good linear relationship with the logarithm concentration of acetamiprid in the range of 5.0 × 10−7 to 1.0 × 10−4 mol/L (0.11335 ppm to 22.67 ppm), with correlation coefficients of 0.97972 and 0.97552, respectively. The calculated LOD and LOQ of this method were 1.19 × 10−7 mol/L (0.265 ppb) and 2.63 × 10−7 mol/L (0.586 ppb), respectively, using SERS signal at 631 cm−1, and 2.95 × 10−7 mol/L (0.657 ppb) and 3.86 × 10−7 mol/L (0.860 ppb) using SERS signal at 1109 cm−1, respectively. Furthermore, the developed SERS method was successfully applied in determining acetamiprid on the surface of apple and spinach. This method offers an exciting opportunity for rapid detection of acetamiprid and other organic pesticides considering its advantages of simple preparation process, good specificity and sensitivity, and short detection time (within 1 h).

Magnetically controlled crystallographic properties of graphite sheets with self-assembled periodic arrays of magnetoelectric nanoparticles

This paper presents an experimental study in which 30-nm CoFe2O4–BaTiO3 core–shell magnetoelectric nanostructures (MENs) were embedded into graphite sheets to enable external control of intrinsic properties such as the intercalation process. The embedded nanoparticles were self-assembled into a honeycomb pattern with a characteristic period on the order of 200 nm, as confirmed through energy-dispersive spectroscopy (EDS) by scanning electron microscopy (SEM) as well as through atomic and magnetic force microscopy (AFM and MFM). Integration of the nanoparticles into the graphite structure was also confirmed through Fourier transform infrared (FT-IR) imaging and X-Ray diffraction (XRD) analysis. XRD measurements indicate crystallographic changes in the response to application of a 500-Oe magnetic field. M-H measurements by vibrating sample magnetometer (VSM) showed the coercivity of the nanoparticles on the order of 250 Oe.

Hysteresis in two dimensional arrays of magnetic nanoparticles

We perform computer simulations to probe the magnetic hysteresis in a two-dimensional (Lx×Ly) assembly of magnetic nanoparticles as a function of dipolar interaction strength hd, temperature T, aspect ratio Ar=Ly/Lx, and the applied alternating magnetic field’s direction. In the absence of magnetic interaction (hd≈0) and thermal fluctuations (T=0 K), the hysteresis follows the Stoner and Wohlfarth model, as expected. For weak dipolar interaction and substantial temperature, the hysteresis has the dominance of superparamagnetic behaviour, irrespective of the applied magnetic field’s direction and Ar. Interestingly, the hysteresis curve has all the characteristics of antiferromagnetic interaction dominance for Ar≤6 and considerable dipolar interaction strength (hd>0.2), independent of applied magnetic direction. When the magnetic field is applied along the system’s shorter axis (x-direction), a non-hysteresis straight line is observed with large hd. In the case of the magnetic field applied along the long axis of the sample (y-direction), ferromagnetic interaction dominates the hysteresis for large hd and Ar>6. Irrespective of hd and applied magnetic field’s direction, the coercive field μoHc and remanence Mr are minimal for Ar≤6 and significant temperature. They are found to increase with hd when Ar is enormous. There is a strong dependence of μoHc and Mr on temperature for weakly interacting MNPs. While for large hd, they depend weakly on temperature. Remarkably, the variation of hysteresis loop area EH as a function of these parameters is the same as that of the coercive field variation. We believe that the concepts presented in this work are relevant in various technological applications such as spintronics and magnetic hyperthermia, in which such self-assembled nanoparticle arrays are ubiquitous.

Surface Lattice Resonances in Self-Assembled Gold Nanoparticle Arrays: Impact of Lattice Period, Structural Disorder, and Refractive Index on Resonance Quality.

Surface lattice resonances are optical resonances composed of hybridized plasmonic and diffractive modes. These collective resonances occur in periodic arrays of plasmonic nanoparticles with wavelength-scale interparticle distances. The appearance and strength of surface lattice resonances strongly depend on the single particle localized surface plasmon resonance and its spectral overlap with the diffractive modes of the array. Coupling to in-plane orders of diffraction is also strongly affected by the refractive index environment and its symmetry. In this work, we address the impact of the interparticle distance, the symmetry of the refractive index environment, and structural imperfections in self-assembled colloidal monolayers on the plasmonic-diffractive coupling. For this purpose, we prepared hexagonally ordered, nonclose packed monolayers of gold nanoparticles using a fast and efficient, interface-mediated, colloidal self-assembly approach. By tuning the thickness and deformability of the polymer shells, we were able to prepare monolayers with a broad range of interparticle distances. The optical properties of the samples were studied experimentally by UV-Vis spectroscopy and theoretically by finite difference time domain simulations. The measured and simulated spectra allow a comprehensive analysis of the details of electromagnetic coupling in periodic plasmonic arrays. In particular, we identify relevant criteria required for surface lattice resonances in the visible wavelength range with optimized quality factors in self-assembled monolayers.

Comparison of hot carrier generation between self-assembled gold and silver nanoparticle arrays tailored to the same hybrid plasmon resonance

We evaluated the properties of hot carrier generation on Au and Ag nanoparticle (NP) 2D arrays by monitoring chemical transformation. The arrays were fabricated by assembling the Au and AgNPs, respectively, with a diameter of ∼30 nm. The plasmon resonance peaks of both the arrays were tuned to around 671 nm, where the intraband transition was the dominant pathway for the surface plasmon excitation since the incident photon energy is below the interband transition threshold for both Au and Ag. Time-resolved surface-enhanced Raman scattering (SERS) spectroscopy was utilized to monitor the changes in the molecular structure sensitively. We selected para-aminothiophenol as the molecule, which was well known to transform to 4,4′-dimercaptoazobenzene (DMAB) by hot carriers generated from the plasmonic excited surface. It was observed that the peak intensity of DMAB increased as the total exposure increased due to the increase in the number of DMAB molecules for both metals, similar to our previous reports. The analysis of the SERS spectra showed that larger laser intensity progressed the transformation more rapidly. The analysis also clarified that the chemical transformation occurs more efficiently on the AgNP array compared to the AuNP array. The superiority in the efficiency for Ag may be derived from contribution of more hot carriers generated in the material with the smaller plasmon damping constant.

Magnetic array-templated method for fabrication of polymer nanoporous films

This paper describes the development of a novel method of producing nanoporous polymeric membranes in a cost-effective and reproducible manner. The novelty of the technique hinges on the exploitation of a new type of sacrificial material & structures - self-assembled arrays of magnetic nanoparticles. The arrays are obtained through application of an external magnetic field to a thin layer of colloidal solution of superparamagnetic nanoparticles in a polymerizable monomer; this is followed by photopolymerisation. The resulting columnar structures form the pore templates which when selectively etched away leave an array of nanopores spanning across the polymeric film. The morphological characterisation of the nanopores by scanning electron microscopy and ionic conductivity revealed a very unusual sponge-like pore morphology. The applications which would benefit from the specific pore morphology and arrayed manufacturing are discussed.

Application of GISAXS in the Investigation of Three-Dimensional Lattices of Nanostructures

The application of the grazing-incidence small-angle X-ray scattering (GISAXS) technique for the investigation of three-dimensional lattices of nanostructures is demonstrated. A successful analysis of three-dimensionally ordered nanostructures requires applying a suitable model for the description of the nanostructure ordering. Otherwise, it is possible to get a good agreement between the experimental and the simulated data, but the parameters obtained by fitting may be completely incorrect. In this paper, we theoretically examine systems having different types of nanostructure ordering, and we show how the choice of the correct model for the description of ordering influences the analysis results. Several theoretical models are compared in order to show how to use GISAXS in the investigation of self-assembled arrays of nanoparticles, and also in arrays of nanostructures obtained by ion-beam treatment of thin films or surfaces. All models are supported by experimental data, and the possibilities and limitations of GISAXS for the determination of material structure are discussed.

Tailoring the interparticle distance in Langmuir nanoparticle films.

The ability to control the interparticle distance in self-assembled arrays of nanoparticles plays an important role in a large number of applications, which require tunable electronic and photonic properties. Importantly, practical applications in real devices rely on arrays satisfying more stringent requirements of lateral homogeneity controlled over a large scale. Herein, the interparticle distance in ordered nanoparticle assemblies was controlled by varying the nanoparticle effective size via the molecular chemical nature and chain length of the ligand. Iron oxide nanoparticles (IONPs) were functionalized by three types of ligands, namely (i) a mixture of oleic acid/oleylamine (OA/OAm), (ii) poly(n-butyl acrylate) (PBA) and (iii) polystyrene (PS), while two different molar masses of PBA and PS were used. The polymeric ligands with narrow dispersity and bearing phosphonic chain-end groups were prepared by atom transfer radical polymerization. Functionalization of the IONPs with polymeric ligands was achieved using a ligand exchange method. Both the hydrodynamic diameter and size distribution of the nanoparticles in colloidal solution were determined by dynamic light scattering (DLS). The mean interparticle distances in Langmuir-Schaefer monolayers prepared on solid substrates were assessed by means of the pair correlation function calculated from the atomic force microscopy (AFM) images. Furthermore, the lateral ordering, homogeneity, and interparticle distances averaged over a mesoscopic scale of the ordered monolayers were studied by the grazing-incidence small-angle X-ray scattering (GISAXS) technique. We demonstrate that the (nanoparticle) centre-to-centre distance in the ordered assemblies constituted by the IONPs with the core diameter of about 6 nm can be varied from 7.6 to about 12 nm with the resulting interparticle gap change by a factor of about 4.

Sputtered SnO2:NiO thin films on self-assembled Au nanoparticle arrays for MEMS compatible NO2 gas sensors

Here, heterostructured Au/SnO2:NiO thin films are fabricated by sputtering SnO2:NiO target onto the self-assembled Au nanoparticle (NPs, diameter ∼ 9.5 nm) arrays and then activated by H2 annealing. Compared with the SnO2 and SnO2:NiO thin film counterparts, the 20 nm thick Au/SnO2:NiO film shows the highest NO2 sensing performance after activated at optimized temperature of 500 °C, with high response of ∼185 to 5 ppm NO2, low detection limit of ∼50 ppb, high selectivity, good stability and also low sensor-to-sensor variation of <15%. The gas sensing property enhancement could not only be attributed to catalytic role of the AuNPs, but also to the effective Schottky barrier and p-n junction formation between Au, SnO2 and NiO, which is verified by the relatively higher Fermi level of ∼4.56 eV compared with those of 4.1–4.3 eV as measured by the ultraviolet photoelectron spectroscopy. Furthermore, this method is of generality to effectively enhance the electron transfer in other sensing materials like pure SnO2 and WO3, showing the promising potency of this Micro-Electrical-Mechanical System (MEMS) compatible heterostucture fabrication method in wafer-scale gas sensor production with high sensitivity, selectivity and good consistency towards low concentration gas detection such as ppb-level NO2.

Self-assembled quasi-hexagonal arrays of gold nanoparticles with small gaps for surface-enhanced Raman spectroscopy.

The fabrication and optical characterization of self-assembled arrangements of rough gold nanoparticles with a high area coverage and narrow gaps for surface-enhanced Raman spectroscopy (SERS) are reported. A combination of micellar nanolithography and electroless deposition (ED) enables the tuning of the spacing and size of the noble metal nanoparticles. Long-range ordered quasi-hexagonal arrays of gold nanoparticles on silicon substrates with a variation of the particle sizes from about 20 nm to 120 nm are demonstrated. By increasing the particle sizes for the homogeneously spaced particles, a large number of narrow gaps is created, which together with the rough surface of the particles induces a high density of intense hotspots. This makes the surfaces interesting for future applications in near-field-enhanced bio-analytics of molecules. SERS was demonstrated by measuring Raman spectra of 4-MBA on the gold nanoparticles. It was verified that a smaller inter-particle distance leads to an increased SERS signal.

Metal Nanoparticle Array as a Tunable Refractive Index Material over Broad Visible and Infrared Wavelengths

Common materials show a limited range of refractive indices over the visible and infrared wavelengths, and their values are not easily tunable once the material is chosen. Here, self-assembled metal nanoparticle arrays are proposed as an effective optical material with a large range of possible refractive indices that are nearly dispersionless over broad wavelength ranges. The material can be potentially fabricated over a large curved surface, and the resulting index is even more tunable by various postprocessing methods, such as material substitution or mechanical stretching. We achieve the highest refractive index of 5.0 at resonance in the visible, exceeding 4.2 over a broadband wavelength regime out of resonance. The key differences from previous studies of self-assembled metal particle arrays are the consideration of the diamagnetic effect and the careful choice of the ligands, which determine the gaps between particles. The sensitivity of the effective index to the size and material of the gap regio...

Effects of particle size and annealing on plasmon-induced charge separation at self-assembled gold nanoparticle arrays.

Two-dimensional periodic Au nanoparticle arrays were constructed on TiO2 thin films by a micelle lithography method and seed-mediated photoelectrochemical growth. Their adjustable interparticle distance allows investigation of a particle size effect on plasmon-induced charge separation (PICS) efficiencies without interference from particle aggregation or plasmon coupling. External or internal PICS efficiencies were found to increase and decrease, respectively, with an increase in particle diameter from 25 to 38 nm. Improvement of the contact between Au nanoparticles and TiO2 by annealing enhanced the intensity of a plasmonic interface mode and both external and internal PICS efficiencies.

Monitoring plasmon coupling and SERS enhancement through in situ nanoparticle spacing modulation.

Self-assembled nanoparticle (NP) arrays at liquid interfaces provide a unique optical response which has opened the door to new tuneable metamaterials for sensing and optical applications. NPs can spontaneously assemble at a liquid-liquid interface, forming an ordered, self-healing, low-defect 2D film. The close proximity of the NPs at the interface results in collective plasmonic modes with a spectral response dependent on the distance between the NPs and induces large field enhancements within the gaps. In this study, we assembled spherical and rod-shaped gold NPs with the aim of improving our understanding of NP assembly processes at liquid interfaces, working towards finely controlling their structure and producing tailored optical and enhanced Raman signals. We systematically tuned the assembly and spacing between NPs through increasing or decreasing the degree of electrostatic screening with the addition of electrolyte or pH adjustment. The in situ modulation of the nanoparticle position on the same sample allowed us to monitor plasmon coupling and the resulting SERS enhancement processes in real time, with sub-nm precision.

Self-Assembled Nanoparticle Arrays on Chemical Nanopatterns Prepared Using Block Copolymer Lithography.

We present a high-throughput and inexpensive fabrication approach that uses self-assembled block copolymer (BCP) films as templates to generate dense nanoscale chemical patterns of polymer brushes for the selective immobilization of Au nanoparticles (NPs). A cross-linked random copolymer mat that contains styrene and methyl methacrylate units serves both as a base layer for perpendicular assembly of nanoscale domains of poly(styrene-block-methyl methacrylate) (PS-b-PMMA) films and as a nonadsorbing background layer that surrounds the chemical patterns. The selective removal of the PMMA block and the underlying mat via oxygen plasma etching generates binding sites which are then functionalized with poly(2-vinylpyridine) (P2VP) brushes. Au NPs with a diameter of 13 nm selectively immobilize on the patterned P2VP brushes. An essential aspect in fabricating high quality chemical patterns is the superior behavior of methyl methacrylate containing cross-linked mats in retaining their chemistry during the grafting of P2VP brushes. The use of BCPs with different molecular weights and volume fractions allows for preparation of chemical patterns with different geometries, sizes, and pitches for generating arrays of single particles that hold great promise for applications that range from molecular sensing to optical devices.

Quantitative label-free and real-time surface-enhanced Raman scattering monitoring of reaction kinetics using self-assembled bifunctional nanoparticle arrays.

Although surface-enhanced Raman scattering (SERS) has proven to be an effective tool for label-free monitoring of catalytic reactions, quantitative characterization of reaction kinetics via this technique remains challenging owing to the difficulty in integrating catalytic and plasmonic activities into a single platform. In this work, we report on an easy access to highly sensitive plasmonic nanoarrays for direct and label-free monitoring of a gold-catalyzed reaction by SERS. The hierarchically structured three-dimensional assemblies, which consist of small gold catalyst nanoparticles distributed on a self-assembled monolayer of larger gold nanoparticles, were formed through a simple and rapid stepwise interfacial self-assembling process (fabrication time <10 min). The well-defined interparticle distances (<1 nm) lead to efficient plasmonic coupling and ensure both catalytic and SERS-active sites exposed to the environment. Such a versatile bifunctional platform thus allows quantitative determination of the rate constant and activation energy of the catalytic reaction with SERS.

Multifunctional Paper Strip Based on Self-Assembled Interfacial Plasmonic Nanoparticle Arrays for Sensitive SERS Detection.

A smart and multifunctional paper-based SERS sensing card is generated through patterning self-assembled interfacial arrays of gold nanoparticles (AuNPs) on the tip of an arrow-shaped paper strip. It is found that the closely packed monolayer of AuNPs is evenly distributed on the paper surface, resulting in a multitude of SERS hot spots over the detection zone. The paper card, with its inherent ability to separate and preconcentrate analytes by the capillary force and polarity difference between sample components, was exploited successfully as an integrated platform, allowing for sub-attomolar (50 × 10(-18) M) detection from microliter-volume (10 μL) samples. Furthermore, the simple preparation (lithography-free process), fast detection (<5 min), and low cost (<3 cents) demonstrate that the paper card is a practical and portable sensing interface for wide application in environmental and food analysis.

Surface-Enhanced Raman Plasmon in Self-Assembled Sulfide-Coated Gold Nanoparticle Arrays

This paper investigates the surface-enhanced Raman plasmon in self-assembled gold nanoparticle arrays. The self-assembly process reported in this paper is triggered by the addition of sulfide in a sample of citrate-stabilized gold nanoparticles (AuNPs). The characterization of gold nanoparticle arrays was carried out by UV-visible absorption spectrum, transmission electron microscopy (TEM), and Raman map. Results demonstrate an aggregation of AuNPs with a peculiar physical docking resembling nanowires. Moreover, these nanostructures exhibited intense Raman scattering signal when compared with regular AuNPs. This simple technique is a candidate for future applications such as sensors for detecting sulfide compounds and nanosystem fabrication.